Quaternary ammonium functionalized cross-linked polyalkylsiloxanes with anti-fouling activity

• US 8,372,384 B2
• Filed: 01/07/2008
• Issued: 02/12/2013
• Est. Priority Date: 01/08/2007
• Status: Expired due to Fees

• Current Assignee: Ndsu-Research Foundation
• Original Assignee: Ndsu-Research Foundation
• Inventors: Chisholm, Bret Ja, Majumdar, Partha, Stafslien, Shane J., Boudjouk, Philip
• Primary Examiner(s): DICKINSON, PAUL W
• Application Number:
  US12/006,926
• Publication Number:
  US 20080181862A1
• Time in Patent Office: 1,863 Days
• Field of Search: None
• US Class Current: 424/78.09
• CPC Class Codes: A01N 33/12 Quaternary ammonium compounds
• CPC Class Codes: A01N 55/00 Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing organo-phosphorus compounds A01N57/00
• CPC Class Codes: A61L 2300/208 Quaternary ammonium compounds
• CPC Class Codes: A61L 2300/404 Biocides, antimicrobial agents, antiseptic agents
• CPC Class Codes: A61L 2300/606 Coatings
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: A61L 29/16 Biologically active materials, e.g. therapeutic substances A61L29/048 takes precedence
• CPC Class Codes: C08L 2666/44 Silicon-containing compounds
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: C09D 183/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• CPC Class Codes: C09D 5/1675 Polyorganosiloxane-containing compositions

Abstract

Functionalized cross-linked polysiloxanes, such as quaternary ammonium terminated cross-linked polyalkylsiloxanes are described herein. The functionalized cross-linked polysiloxanes may be used in an antifouling composition to prevent biological fouling in aqueous and/or marine environments.

Claims

1. A polymeric material formed by reacting a mixture comprising:

(a) alkoxysilyl functionalized quaternary amine, wherein the alkoxysilyl functionalized quaternary amine comprises alkoxysilyl functionalized quaternary amine having an N—

(C16-C20)-n-alkyl-N,N-dimethylamino group;

(b) silanol terminated polysiloxane; and

(c) trifunctional silane, tetra-functional silane, or a mixture thereof;

wherein the mixture comprises about 0.001 to 0.05 moles of the alkoxysilyl functionalized quaternary amine per 100 gm of the silanol terminated polysiloxane.

2. The polymeric material of claim 1, wherein the alkoxysilyl functionalized quaternary amine comprises trialkoxysilyl functionalized quaternary amine.

3. The polymeric material of claim 1, wherein the trifunctional silane comprises alkyltriacyloxysilane.

4. The polymeric material of claim 1, wherein the trifunctional silane comprises acyloxysilane, ketoxime-based silane, or a mixture thereof.

5. The polymeric material of claim 1, wherein the alkoxysilyl functionalized quaternary amine comprises bis-(trialkoxysilyl functionalized)-quaternary amine.

6. The polymeric material of claim 1 wherein the alkoxysilyl functionalized quaternary amine comprises trialkoxysilyl functionalized, tetraalkyl-quaternary amine.

7. The polymeric material of claim 1 wherein the alkoxysilyl functionalized quaternary amine comprises N,N-bis(trialkoxysilylalkyl)-N,N-dialkylamine.

8. The polymeric material of claim 1 wherein the silanol terminated polysiloxane has a formula

11. The polymeric material of claim 1 wherein the mixture further comprises a filler.

12. The polymeric material of claim 11 wherein the filler comprises silica.

13. The polymeric material of claim 1 wherein the mixture further comprises about 5 to 15 wt. % silica.

14. The polymeric material of claim 8 wherein m is 0;

and the silanol terminated polysiloxane has a molecular weight of about 1,000 to 50,000.

15. The polymeric material of claim 1 wherein the mixture comprises at least 0.015 moles of the alkoxysilyl functionalized quaternary amine per 100 gm of the silanol terminated polysiloxane.

16. The polymeric material of claim 1 wherein the alkoxysilyl functionalized quaternary amine further comprises a trialkoxysilyl functionalized quaternary amine having an N—

(C12-C14)-n-alkyl-N,N-dimethylamino group.

17. The polymeric material of claim 8 wherein the silanol terminated polysiloxane has a molecular weight of about 1,000 to 50,000;

m is 0; and

R⁷, R⁸, and R⁹ are methyl;

alkoxysilyl functionalized quaternary amine further comprises a trialkoxysilyl functionalized quaternary amine having an N—

(C12-C14)-n-alkyl-N,N-dimethylamino group; and

the trifunctional silane comprises tri-functional acyloxysilane.

18. The polymeric material of claim 17 wherein the alkoxysilyl functionalized quaternary amine comprises a quaternary amine having a formula

Trimethoxysilyl-R′

—

N⁺R¹R²R X⁻

wherein R¹ and R² are methyl;

R is an n-alkyl group having 12 to 20 carbon atoms;

R′

is a propylene and/or ethylene group; and

X is chloride and/or bromide.

21. The polymeric material of claim 1 wherein the mixture comprises about 0.005 to 0.03 moles of the alkoxysilyl functionalized quaternary amine per 100 gm of the silanol terminated polysiloxane.

23. The polymeric material of claim 8 wherein the silanol terminated polysiloxane has a molecular weight of about 10,000 to 75,000 and has a formula

24. The polymeric material of claim 23 wherein the silanol terminated polydialkylsiloxane has a molecular weight of about 15,000 to about 50,000;

the alkoxysilyl functionalized quaternary amine includes

trialkoxysilyl-R′

—

N⁺R¹R²R X⁻

wherein R¹ and R² are methyl;

R is an alkyl group having 16 to 20 carbon atoms;

R′

is a propylene and/or ethylene group; and

X is a halide; and

the mixture comprises 0.01 to 0.03 moles of the alkoxysilyl functionalized quaternary amine per 100 gm of the silanol terminated polysiloxane.

25. The polymeric material of claim 1 wherein the silanol terminated polydialkylsiloxane has a molecular weight of about 15,000 to about 50,000;

and the mixture comprises 0.01 to 0.03 moles of the alkoxysilyl functionalized quaternary amine per 100 gm of the silanol terminated polysiloxane.

26. The polymeric material of claim 17 wherein the tri-functional acyloxysilane comprises methyltriacetoxysilane.

9. A substrate having an antifouling coating on a surface thereof;

wherein the coating comprises a cross linked polymer formed by reacting a mixture comprising trifunctional silane, tetra-functional silane, or a mixture thereof;

alkoxysilyl functionalized quaternary amine; and

silanol terminated polysiloxane;

wherein the mixture comprises about 0.001 to 0.05 moles of the alkoxysilyl functionalized quaternary amine per 100 gm of the silanol terminated polysiloxane; and

the alkoxysilyl functionalized quaternary amine comprises alkoxysilyl functionalized quaternary amine having an N—

(C16-C20)-n-alkyl-N,N-dimethylamino group.

19. The substrate of claim 9 wherein the silanol terminated polysiloxane has a molecular weight of about 15,000 to 50,000;

and R⁷, R⁸, and R⁹ are methyl;

the alkoxysilyl functionalized quaternary amine comprises a quaternary amine having a formula

Trimethoxysilyl-R′

—

N⁺R¹R²R X⁻

wherein R¹ and R² are methyl;

R is an n-alkyl group having 16 to 20 carbon atoms;

R′

is a propylene and/or ethylene group; and

X is chloride and/or bromide; and

the mixture comprises tri-functional acyloxysilane.

27. The polymeric material of claim 19 wherein the tri-functional acyloxysilane is alkyltriacyloxysilane.

10. A substrate having an antimicrobial polymer coating on a surface thereof, the coating comprising:

quaternary amino functionalized cross-linked polysiloxane formed by reacting a mixture comprising;

trifunctional silane, tetra-functional silane, or a mixture thereof;

alkoxysilyl functionalized quaternary amine; and

silanol terminated polysiloxane;

wherein the mixture comprises about 0.001 to 0.05 moles of the alkoxysilyl functionalized quaternary amine per 100 gm of the silanol terminated polysiloxane; and

the alkoxysilyl functionalized quaternary amine comprises alkoxysilyl functionalized quaternary amine having an N—

(C16-C20)-n-alkyl-N,N-dimethylamino group.

20. The substrate of claim 10 wherein the silanol terminated polysiloxane has a molecular weight of about 15,000 to 50,000;

the alkoxysilyl functionalized quaternary amine comprises a quaternary amine having a formula

Trimethoxysilyl-R′

—

N⁺R¹R²R X⁻

wherein R¹ and R² are methyl;

R is an n-alkyl group having 16 to 20 carbon atoms;

R′

is a propylene and/or ethylene group; and

X is chloride and/or bromide; and

the mixture comprises tri-functional acyloxysilane.

28. The polymeric material of claim 20 wherein the tri-functional acyloxysilane is alkyltriacyloxysilane.

22. A cross-linked polymeric material formed by reacting a mixture comprising:

(a) alkoxysilyl functionalized quaternary amine comprising trialkoxysilyl functionalized quaternary amine having an N—

(C16-C20)-n-alkyl-N,N-dimethylamino group; and

(b) silanol terminated polysiloxane;

wherein the mixture comprises about 0.001 to 0.05 moles of the alkoxysilyl functionalized quaternary amine per 100 gm of the silanol terminated polysiloxane.